Method fob converting higher-boiling petroleum hydrocarbons into



G. W. GRAY. NG HIGHER BOILING PETROLEUM HYDROCARBONS BOILING PETROLEUM HYDROCARBONS.

INTO LOWER METHOD FOR CONVERTI APPLICATION FILED MN. 23. 1913. p 1 ,1. 93,540. Patented Aug. 8, i916.

UNITED STATES PATENT oFFI'o GEORGE wiLLIA GRAY, 0F HOUSTON, TEXAS.

METHOD FOR CONVERTING HIGHER-BOILING PETROLEUM HYDROCARBONS INTO LOWER-BOILING PETROLEUM HYDROCARBONS.

Specification of Letters Patent.

Patented Aug. 8, 1916.-

' Application filed January 23, 1913. Serial No. 743,713.

To all whom it may concern Be it known that I, GEORGE WILLIAM GRAY, a citizen of the United States, residing at Houston, in the county of Harris and State of Texas, have invented certain new and useful Improvements in Methods for Converting Higher'Boiling Petroleum Hydrocarbons into Lower-Boiling Petroleum Hydrocarbons, of which the following is a specification.

My invention consists in novel methods for converting higher-boiling petroleum hydrocarbons of complex molecules into lowerboiling petroleum hydrocarbons of a simpler molecule.

I have discovered that substantially all the higher-boiling hydrocarbons can be con verted into naphtha or gasolene if they be heated, in the presence of a suitable agent, to a temperature not substantially above the end-boiling-point of naphtha.

N aphtha is a general term which includes a number of different grades of gasolene.

' .Naphtha, illuminating oils, etc, are made up of individuals having diflerent boiling points. In making a distillation test on a sample of naphtha or gasolene, for example, a quantity is introduced into a flask provided with a thermometer, the outlet of the flask being connected to a condenser.- Heat is gradually applied. The temperature at which the first liquid drops into the receiving flask is called the initial boiling point. From time to time as the flow of liquid ceases, the temperature is slightly raised. The temperature at which no oil is left in the flask is called the end boiling point. (iasolene or naphtha is a product which will begin to distil anywhere from about 70 to 150 F., and will all distil oif below a te1n perature of about 350 to 400 ll; while illuminating oil is a product which will begin to distil anywhere from about 310 to 320 l and will all distil otf below a temperature of about (300 F. The term end boiling point in the specification and claims is used to designate the highest boiling point of any of the constituouts of eol'nmercial naphtha or illuminating definite figures can be given. For example, it is a matter of common knowledge that as the demand for naphtha or gasolene has in creased much more rapidly than the demand for illuminating oil and as improvements point hydrocarbons may be, if desired, con- \erted into hydrocarbons having boiling po nts not above that temperature; and if the temperature is maintained not above 350 F.. substantially the whole body may be, if desired, converted into hydrocarbons having boiling-points not above that temperature. The same principle exactly would apply if, in the future, connnercial naphtha should include constituents having boilin points as high as 400 F., or higher.

As an example. I may take 100 parts of petroleum distillate freed from naphtha prmhictssuch as gas oil made from a paratiin or semiqiaratlin or semi-asphalt crude oil and add to it 5 parts of a suitable agentsuch as anhydrous aluminum chlorid, for example. The mixture is then heated to a temperature at which the vapor given off is not substantially above 325 degrees to 350 degrees F. The still is pref rably provided with stirring apparatus f any known and approved form to keep the aluminum chlorid in suspension and in intimate contact with the oil. andto prevent over-heating it. Preferably also fresh changes of oil are added from time to time as the charge becomes low. to avoid distilling the contents to dryness. and to obtain the advantage of 'the' repeated use of the reducing agent. the

efficiency of which appears to persist for a considerable time. If the charge were distilled to dryness, the agent would be lost, coke would be formed and the cleaning of the still after each charge would be re( uired. If desirable. additional aluminum clilorid may be added from time to time, as required. The use of a larger percentage of anhydrous aluminum chlorid than that named in the above e.\ amplesay 10 parts to 100 parts of oil, for example-ca'uses the desired reactions to take place much more rapidly. The result of the process is to break up the complex molecules of the oil into the simpler molecules of naphtha or gasolene, which passes to a suitable condensing apparatus, and is there collected. In this way I have converted the entire body of the oil into naphtha or gasoleneand gases and have recovered from- 70 to 80 percent. in the form of naphtha or gasolene, the remainder being converted into gases which escaped, or was left in the still in the form of coke and ,organic matters.

\VhileI am not able at the present time to give an account of the reactions which take place, present information suggests that the action of the agent vis whollyor partially catalytic. There is, however, some loss of the agent by con'ibii'u'itio'n or reaction with impurities in the oil-sueh. for example, as by reaction with the sulfur present. which is indicated by'the stroi'ig' odor of lrvdrogen sulfid and perhaps by combination with gasolene the oil itself. ()ther equivalent agents may be used in -ombin.-1tion with", or in m-ear, anhydrous aluminum chlori'dsuch, for example, as anlrwlrous ferric chlorid, and, perhaps, other substances which, up to the present, I have not had time to try. The use of equivalent agents is includedwithin the scope of my claims. I have found anhydrous ferric chlorid to be a less active agent than anhydrous aluminum chlorid and that it is necessary to use larger qu ntities of it to effect the same result.

J ll'hen the temperature of the vaporis not raised above about 3'35 degrees to 350 degrees l., or even somewhat higher, the naphtha produced can bc'sold directly in commerce at the present time as automobile or stove gasole'ne. and the endboiling-point of such gasolenc is continually rising; or it may be redistilled and separated into gasolencs of dill'ercnt gravities in the usual manner. It is superior to the naphtha or produced by direct distillation from crude oil in that it is substantially free from unsaturated lrydrocarb ons, as is shown y the well-known sulfuric acid test. The j |-o above described may also be. practised with illuminating oil or lubricating oil as starting materials. lt may also be practisedwith crude oil as the starting material.

but it is less :nlva'nt'agcoils to use. crude. oil

becauseit its contained impiu'ities.

instead of maintaining the still at the low tcm rcratures above described. l mav in-' crease the tem wraturo up to about 550 degrccs 'to (Kill degrees 'l"., in which case the distillate consists of naphtha and il'lum'i'nat lug oil, which may bc. separated by l'rae tiollul' distillation in the usual way. Not

be driven olf, resulting not only in loss of I that agent, but also in clogging the pipes.

In the drawing I have shown one form of still which is suitable for use in the practice of my process, although it will be understood that any other form of still which is suitable may be used.

In the drawin is the still.

B is a shaft rotated by a pulley O and gears l). The shaft l3 carries stirring blades l), I, the lower blades ll' carrying depending chains p (l are spash plates attachedto the shell of the still.

It is a manhole, and I a discharge opening at the bottom. v

.l is the vapor exhaust pipe, and K is an inlet pipe' for oil and'chciuilials.

\l'hatl claim and desire 'to'seeure by Letters Patent of the United States 'is:-

l. The process of converting hydrocarbons having higher-lmiling-points into naphtha, which consists in heating said hydrocar-bons in the presence of anhydrous aluminum chlorid to a temperature producing vapor having a temperature not substantially above the eml-boiling-point of naphtha aml maintaining them at such temperature.

The process, of converting hydrocarbons having higher-b'oiling-points into h \'di"ocarlmus having lower-boiling-points.

which consists in heating said hydrocarbons 'czll'bons having higher boiling-points into lrvilrocarlmns having lower luiili||; pniuts, which consists in heating said hydrm'arbons process of converting hydroin the presence 1 anhydrous aluminum ehlurid, in a temperature prmlueing vapor having a tem wralure not substantially above the eiul-lmlling-puint of illuminating oil and maintaining sueh \apor temperature until the greater part of the oil has been \KIHll'illPll as naphtha alul illuminating oil.

In testinmny whereof I have hereunto signed my name in the presence of two subserihiug witnesses.

GEORGE \YI LLIAM GRAY.

\Vituesses:

J. EDGAR BKLL, M. E. MQNLNCIL 

